This paper examines whether retention of partially hydrolyzed polyacrylamide (HPAM) is different under anaerobic versus aerobic conditions. Both static (mixing with loose sand) and dynamic methods (core floods) were used to determine HPAM retention. There are both advantages and disadvantages associated with determining polymer retention using static tests versus dynamic tests and using aerobic versus anaerobic conditions. From static retention measurements, polymer adsorption values on pure silica sand or Berea sandstone were small, and they showed little difference between experiments conducted aerobically or anaerobically. For both aerobic and anaerobic conditions, HPAM retention increased significantly with increased pyrite or siderite content. Static retention under anaerobic conditions ranged from 45-75 µg/g with 1% of either pyrite or siderite to 137-174 µg/g for 10% pyrite or siderite to 1161-1249 µg/g for 100% pyrite or siderite.

If iron minerals are present, the most representative polymer retention results are obtained (for both static and dynamic tests) if conditions are anaerobic. Retention values (from static measurements) under aerobic conditions were commonly twice those determined under anaerobic conditions. If iron minerals are present and retention tests are performed under aerobic conditions, TOC or some similar method should be used for polymer detection. Viscosity detection of polymer may provide retention values that are too high (because oxidative degradation can be misinterpreted as polymer retention). For a broad range of siderite content, retention from static tests did not depend on whether dissolved oxygen was present. However, for a broad range of pyrite content, HPAM retention was significantly lower in the absence of dissolved oxygen than under aerobic conditions. Theses results may be tied to iron solubility. When polymer solutions were mixed with 100% pyrite over the course of 12 hours, 360–480-ppm iron dissolved into polymer solutions under both aerobic and anaerobic conditions, whereas with 100% siderite, only 0–0.6-ppm iron dissolved. If dynamic methods (i.e., corefloods) are used to determine polymer retention under aerobic conditions, flow rates should be representative of the field application. Rates that are too high lead to underestimation of polymer retention. With 10% pyrite, dynamic retention was 211 µg/g at 6 ft/d versus 43.2 µg/g at 30 ft/d. In contrast, retention values were fairly consistent (40.6 – 47.8 µg/g) between 6 ft/d and 33 ft/d under anaerobic conditions.

Post-fracturing production data analysis indicates stimulation of some west Texas wells with surfactant additives did not enhance production as high as expected. Analysis of flowback and produced water for surfactant residues revealed 99% of surfactant was retained inside wells (Rane and Xu 2015). This indicates surfactant plating out on rock in the near-wellbore (NWB) region, restricting travel deeper into the reservoir, which compromises well performance. This study presents a sacrificial agent (SA) to cover rock surface near the wellbore, allowing surfactant to penetrate the formation.

Literature precedent exists that polyelectrolyte (PET)-based SAs could significantly reduce surfactant adsorption not only onto a variety of outcrop minerals (Carlpool dolomite, calcite, kaolinite, Berea sandstone, Indiana limestone, etc.) and metal oxide nanoparticles, but also unconventional shale formulations in which surface area can be up to 700 m2/g. In this study, the adsorptions of surfactant and SA to proppants were first examined. Results indicate no adsorption was observed to proppant for both surfactants and PET-based SAs. SAs (0.5 to 1 gal/1,000 gal (gpt)) were then injected with surfactant (1 to 3 gpt) at an appropriate ratio into column-packed shale formulations (primarily composed of calcite, dolomite, quartz, illite, pyrite, and plagioclase feldspar) to investigate its effectiveness in controlling surfactant retention caused by adsorption. Laboratory testing revealed injection of 3 gpt mixture of surfactant and SA has a similar adsorption profile (surface tension as a function of time) as 3 gpt surfactant alone based on the dynamic surface tension measurement. Notably, the addition of SAs resulted in lower surface tension and enhanced hydrocarbon solubility; and thus, an improved oil recovery by surfactant was achieved as evidenced by the oil recovery tests. Additionally, 68% friction reduction of the fracturing fluid with surfactant and SA was sufficient for the field operation compared to the guar-based fluid used in the hydraulic fracturing applications.

As a result of the laboratory findings, field trials were executed on a three well pad in the Permian basin (PB). For the first 30 days oil and gas production appeared to be significantly higher than the average production from offset wells in the same area that were previously fractured with the same surfactant.

The immense nanotechnology advances in other industries provided opportunities to rapidly develop various applications of nanoparticles in the oil and gas industry. In particular, nanoparticle has shown its capability to improve the emulsion stability by generating so-called Pickering emulsion, which is expected to improve EOR processes with better conformance control. Recent studies showed a significant synergy between nanoparticles and very low concentration of surfactant, in generating highly stable emulsions. This study's focus is to exploit the synergy's benefit in employing such emulsions for improved mobility control, especially under high-salinity conditions.

Hydrophilic silica nanoparticles were employed to quantify the synergy of nanoparticle and surfactant in oil-in-brine emulsion formation. The nanoparticle and/or the selected surfactant in aqueous phase and decane were co-injected into a sandpack column to generate oil-in-brine emulsions. Four different surfactants (cationic, nonionic, zwitterionic, and anionic) were examined, and the emulsion stability was analyzed using microscope and rheometer.

Strong and stable emulsions were successfully generated in the combinations of either cationic or nonionic surfactant with nanoparticles, while the nanoparticles and the surfactant by themselves were unable to generate stable emulsions. The synergy was most significant with the cationic surfactant, while the anionic surfactant was least effective, indicating the electrostatic interactions with surfactant and liquid/liquid interface as a decisive factor. With the zwitterionic surfactant, the synergy effect was not as great as the cationic surfactant. The synergy was greater with the nonionic surfactant than the zwitterionic surfactant, implying that the surfactant adsorption at oil-brine interface can be increased by hydrogen bonding between surfactant and nanoparticle when the electrostatic repulsion is no longer effective.

In generating highly stable emulsions for improved control for adverse-mobility waterflooding in harsh-condition reservoirs, we show a procedure to find the optimum choice of surfactant and its concentration to effectively and efficiently generate the nanoparticle-stabilized emulsion exploiting their synergy. The findings in this study propose a way to maximize the beneficial use of nanoparticle-stabilized emulsions for EOR at minimum cost for nanoparticle and surfactant.

Recent studies on the use of ammonia as an alkali for performing alkali-surfactant-polymer (ASP) floods have shed light on its advantages over conventional alkalis such as lower alkali requirements, ease of transportation and storage. This study is aimed towards understanding surfactant adsorption in sandstone and carbonate rocks in the presence of ammonia. Zeta potential measurements were performed to characterize Bandera brown sandstone and Silurian dolomite surfaces in the presence of ammonia and sodium carbonate. A series of experiments were performed with and without ammonia such as static surfactant adsorption experiments on crushed Bandera brown sandstone and Silurian dolomite rocks, single phase surfactant transport experiments in sandstone and carbonate cores, surfactant phase behavior to identify an ultra-low interfacial tension (IFT) surfactant formulation, and oil recovery coreflood experiments using these surfactant formulations. Zeta potential measurements showed a reduction in zeta potential of Bandera brown and Silurian dolomite by adding ammonia to increase the pH. Surfactant adsorption experiments showed that ammonia was able to reduce the adsorption on sandstones, but not much difference was observed for carbonates. The ultra-low IFT surfactant formulations developed with and without ammonia showed very similar phase behavior. High oil recoveries and very low surfactant retentions were observed in the oil recovery experiments performed in sandstones.

An important factor during the life of a heavy crude reservoir is the oil mobility. It depends on two factors, oil viscosity and oil relative permeability. Two characteristics of nanoparticles that make them attractive for assisting IOR and EOR processes are their size (1 to 100 nm) and ability to manipulate their behavior. Due to their nano-sized structure, nanomaterials have large tunable specific surface areas that lead to an increase in the proportion of atoms on the surface of the particle, indicating an increasing in surface energy. Nanoparticles are also able to flow through typical reservoir pore spaces with sizes at or below 1 micron without the risk to block the pore space. Nanofluids or "smart fluids" can be designed by tuning nanoparticle properties, and are prepared by adding small concentrations of nanoparticles to a liquid phase in order to enhance or improve some of the fluid properties. However the use of nanoparticles and nanofluids for oil mobility has been poorly studied. Hence, the scope of this work is to present the field evaluation of nanofluids for improving oil mobility and mitigate alteration of wettability in two Colombian heavy oil fields; Castilla and Chichimene. Asphaltenes sorption tests with two different types of nanomaterials were performed for selecting the best nanoparticle for each type of oil. An oil based nanofluid (OBN) containing these nanoparticles was evaluated as viscosity reducer under static conditions. Displacement tests through a porous media in core plugs from Castilla and Chichimene at reservoir conditions were also performed. OBN was evaluated to reduce oil viscosity varying oil temperature and water content. Maximum change in oil viscosity is achieved at 122°F and 2% of nanofluid dosage. The use of the nanofluid increased oil recovery in the core flooding tests, caused by the removal of asphaltenes from the aggregation system, reduction of oil viscosity, and the effective restoration of original core wettability. Two field trials were performed in Castilla (CNA and CNB wells), by forcing 200 bbl and 150 bbl of nanofluid respectively as main treatment within a radius of penetration of ~3 ft. Instantaneous oil rate increases of 270 bopd in CNA and 280 bopd in CNB and BSW reductions of ~11% were observed. In Chichimene also two trials were performed (CHA and CHB), by forcing 86 bbl of and 107 bbl of nanofluid as main treatment within a radius of penetration of ~3 ft. Instantaneous oil rate increases of 310 bopd in CHA and 87 bopd in CHB were achieved not BSW reduction has been observed yet. Interventions were performed few months ago and long term effects are still under evaluation. Results look promising making possible to think extending application of nanofluid in other wells in these fields.

Preliminary studies have been done to characterize rock-fluid properties, and flow mechanisms in the shale reservoirs. Most of these studies, through modifying methods used for conventional reservoirs, fail to capture dynamic features of shale rock and fluids in confined nano-pore space. In unconventional reservoirs, interactions between the wall of shale and the contained fluid significantly affect phase and flow behaviors. The inability to model capillarity with the consideration of pore size distribution characteristics using commercial software may lead to an inaccurate oil production performance in Bakken. This paper presents a novel formulation that consistently evaluates capillary force and adsorption using pore size distribution (PSD) directly from core measurements. The new findings could better address differences in flow mechanisms in unconventional reservoirs, and thus lead to an optimized IOR practice.

Sandstone reservoirs containing significant amount of clays (30-40 wt%) with moderate permeability (20-50 mD) provide a unique challenge to surfactant based enhanced oil recovery (EOR) processes. A critical risk factor for these types of reservoirs is adsorption of surfactants due to greater surface area attributed to clays. Clays also have high cation exchange capacity (CEC) and can release significant amounts of di-valents that lead to increased retention of the surfactant. These factors could adversely affect the economics of a flood.

We present a case study where a robust formulation was designed and tested in lab/field for a reservoir located in Wyoming, USA and contains up to 35-40 wt% clays (predominately Kaolinite and Illite). The residual oil saturation is high (Sor=0.4) while the permeability of the formation is between 20-50 mD. The reservoir has been waterflooded historically with low salinity water which has led to formation permeability damage. Due to high levels of clays, adsorption of the surfactant on the rock surface was determined to be between 3-4 mg/g rock by static adsorption tests.

This publication demonstrates how the following challenges have been successfully addressed in the lab as well as in the field in the form of single well chemical tracer test (SWCTT).

Designed a robust alkaline-surfactant-polymer (ASP) formulation that showed ultra-low interfacial tension (IFT) values and aqueous solubility remains soluble in the aqueous solution over a broad range of salinity.

Mitigated surfactant adsorption issues to make the cEOR solution economic. A sacrificial agent was identified that acted synergistically with alkali and also did not alter the optimum salinity of the formulation.

Performed restored state core analysis using the available damaged core material. The main challenge being restoration of the coreplugs to current reservoir conditions for coreflood experiment without causing additional formation damage due to injection of low salinity formation brine.

Designed a flood that utilized a pre-flush to provide a favorable salinity gradient and to inject sacrificial agent ahead of the surfactant front.

Performed polymer screening to select right molecular weight of polymer so that the right balance of mobility control and injectivity in the reservoir can be obtained.

Heavy (HO) and extra–heavy oil (EHO) production is complicated due to its high asphaltene content that lied to adverse rheological properties. In addition, the upgrading of these unconventional oils at surface or sub-surface conditions is a low cost-effective process because of the large amounts of energy needed. Accordingly, several in-situ techniques for enhancing HO and EHO recovery with objective of upgrading the oil and improving its viscosity and mobility have been employed. In this sense, nanoparticulated catalysts have demonstrated a synergistic effect in the enhancement of oil recovery and the improvement of the pyshicochemical properties of HO and EHO such as viscosity, API gravity and content of heavy hydrocarbons such as asphaltenes. Hence, this work aims at investigate the effect of catalytic active nanoparticles in the improvement of the efficiency in recovery of a continuous steam injection process.

Nanoparticles were selected trough batch-adsorption experiments and the subsequent evaluation of the temperature for catalytic steam gasification in a thermogravimetric analyzer. A nanoparticulated support was functionalized with 2 wt% of NiO and/or PdO nanocrystals in order to improve the catalytic activity of the nanoparticles.

Also, successfully a methodology for evaluating the effect of nanoparticulated catalyst in processes of continuous vapor injection was developed. Oil recovery was evaluated using a slim tube filled with a non-confined sand pack in steam injection scenarios in absence and presence of a water-based nanofluid. The displacement test was carried out by (1) constructing the base curves, (2) estimating the oil recovery by the continuous injection of vapor in absence of nanofluid and (3) identifying the influence of the nanoparticles in the enhanced recovery of oil.

It was found that functionalized nanoparticles lead to higher adsorption of asphaltenes, higher degrees of asphaltenes self-association and lowered the temperature of n-C7 asphaltenes steam gasification. It was also observed that the oil recovery increased up to 46% for the system assisted by nanoparticles in comparison with the vapor injection without the nanocatalyst. API gravity of crude oil increased from 7.2 to 12.1°. A reduction of 59% in oil apparent viscosity was also observed. Additionally, trough n-C7 asphaltene and residue content it was demonstrated that nanoparticles are an excellent alternative for HO and EHO upgrading in processes involving vapor injection. n-C7 asphaltene content decreased a 5.2 percentile points after vapor injection in presence of nanoparticles in comparison with the virgin EHO. Also, the residue content (620°C+) decreased a 47%. Improved oil recovery due to nanoparticles injection could be attributed to three main reasons: i) wettability alteration of the porous media, ii) viscosity reduction due to reduction of the asphaltene aggregate and iii) crude oil upgrading. This study should generate a better landscape about the use of catalytic nanoparticles in the improvement of enhanced oil recovery processes and its application in local and international scenarios.

This is the final installment in a series of three papers examining iron mineralogy and its effect on surfactant adsorption in reservoir and outcrop rock samples. The goal of these studies is to establish best practices for obtaining surfactant adsorption values representative of those in a reduced oil reservoir, despite performing experiments in an oxidizing laboratory atmosphere.

This article follows two others examining the abundance and form of iron in the reservoir and in core samples (Part I: Levitt et al., 2015), and a proposed core restoration technique utilizing iron-reducing bacteria (Part II: Harris et al., 2015). In this Part III, chemical reduction methods are examined.

Surfactant retention is a leading uncertainty in economic forecasting of chemical EOR, in large part due to the order-of-magnitude effects of artifacts such as improper core preservation. The industry standard is to (a) limit atmospheric contact of cores to the extent feasible, and (b) when necessary, reduce oxidized cores using strong reducing agents such as sodium dithionite, along with buffering and chelating agents such as sodium bicarbonate and EDTA or sodium citrate. However few studies have been performed to determine whether such invasive treatments are necessary, or what unintended effects the use of such reactive chemicals may have.

The most striking conclusion from these studies is the lack of clear evidence of any advantage of electrochemical reduction versus a simpler treatment with chelators such as sodium citrate or EDTA. Wang (1993) suggests that oxidation of reservoir cores leads to higher surfactant adsorption due to the reduction of clays, which yields a more negative surface charge. Static experiments with montmorillonite clay, as well as an oxidized outcrop containing significant clay and iron content, illustrate that rinsing with non-reducing agents such as sodium bicarbonate, EDTA, or sodium citrate can lower adsorption as much as a strong reducing agent such as sodium dithionite. In the case of montmorillonite, cation exchange appears to be the mechanism by which adsorption is lowered, and so NaCl alone is sufficient to lower adsorption to near-zero values. For the iron- and clay-containing outcrop material, initial measurements indicating "adsorption" far in excess of a dense bilayer were due in fact to the precipitation of sulfonate surfactant with calcium, which eluded from the dissolution of small amounts of anhydrite. An alkyl alkoxy sulfonate surfactant showed higher calcium tolerance, and did not yield "multilayer" adsorption when equilibrated with the anhydrite-containing core sample.

While treatment with a citrate-bicarbonate-dithionite solution does indeed lower adsorption several-fold further, solutions of either sodium bicarbonate or EDTA are at least as effective, and sodium citrate is almost as effective. These non-reductive treatments remove small amounts (~0.1% – ~0.2% of rock mass) of Fe and Al, and fines are invariably apparent in treatment fluids, both of which suggest removal of small amounts of trivalent Fe/Al colloids. Wang (1993) suggests reduction or removal of trivalent iron from clay surfaces as a possible mechanism of lowered adsorption under electrochemically reducing conditions. These results suggest that removal of trivalent cations, with concomitant lowering of anionic surfactant adsorption, is possible with non-reductive chelators such as sodium citrate or sodium EDTA. Sodium bicarbonate is equally effective at lowering adsorption, but does not result in elution of Fe or Al, indicating that these are likely reprecipitated. PIPES buffer, which is used in biological applications for its low propensity to form ligands, lowers adsorption as much and no more than a 10% NaCl rinse, suggesting only anhydrite removal and possibly cation exchange with clays occurs.

While these results suggest that non-reductive means may be used to remove artifacts introduced by core oxidation, they come with an important caveat: even rinsing with a brine solution can result in significant alteration of mineralogy. The use of chelating agents will invariably result in dissolution of any soluble minerals present such as gypsum or anhydrite, which can be an important contributor to surfactant (in particular ABS) consumption.

In cases where iron removal is necessary due to polymer degradation issues, PIPES buffer is proposed for use as an alternative to bicarbonate, the latter having a greater tendency for ligand formation. The combination of borohydride and bisulfite is suggested as an alternative to dithionite as a reducing agent, resulting in more complete iron removal under some conditions, and anecdotally less tendency for polymer degradation upon subsequent oxidation, though both of these claims should be verified.

The chemical cost to recover an incremental barrel of oil is directly proportional to the surfactant retention, so the single most effective way to reduce the cost is to reduce surfactant retention. The main objective of this research was to demonstrate how surfactant retention could be reduced to almost zero by careful optimization of the chemical formulations for different crude oils. Although surfactant retention has been studied for many years over a wide range of reservoir conditions, its dependence on the rheological behavior of the microemulsion that forms in-situ has not been adequately studied. Thus, in this paper we emphasize the importance of microemulsion rheology and demonstrate how to develop and test formulations with properties that give very low surfactant retention. Novel co-solvents (iso-butanol (IBA) alkoxylates and phenol alkoxylates) were tested in some of the formulations with excellent results. Unlike classical co-solvents used to optimize chemical formulations, the new co-solvents cause only a slight increase in the interfacial tension. A series of ASP corefloods were performed in sandstone cores with and without oil to measure surfactant and co-solvent retention and to elucidate the effects of microemulsion viscosity, salinity gradient, clay content, surfactant concentration and other variables. Dynamic adsorption was measured in cores with the same mineralogy and compared with the retention from oil recovery corefloods to determine the component of the retention due to phase trapping.